Abstract
This account summarizes our studies of [2,3]-sigmatropic rearrangements of vinylaziridines and allylic amines. The scope and limitations of the reactions as well as our present mechanistic understanding are also discussed.
1 Introduction
2 Aza-[2,3]-Wittig Rearrangement of Vinylaziridines
2.1 Early Attempts
2.2 Synthesis of Vinylaziridines
2.3 Rearrangement of Vinylaziridines
2.4 Total Synthesis of Indolizidines (-)-209B and (-)-209D
3 [2,3]-Sigmatropic Rearrangement of Allylic Amines
3.1 Lewis Acid Mediated Rearrangements
3.2 Asymmetric Rearrangements
4 Conclusions
Key words
rearrangements - vinylaziridines - ylides - pericyclic reactions - asymmetric reactions
References and Notes
1 Nakai K.
Mikami K.
Org. React.
1994,
46:
105
2 Marshall JA. In Comprehensive Organic Synthesis
Vol. 3:
Trost BM.
Fleming I.
Pergamon;
Oxford:
1991.
p.975-1014
3 Mikami K.
Nakai T.
Synthesis
1991,
594
4 Vogel C.
Synthesis
1997,
497
5 Reetz MT.
Schinzer D.
Tetrahedron Lett.
1975,
16:
3485
6 Durst T.
Elzen RVD.
LeBelle MJ.
J. Am. Chem. Soc.
1972,
94:
9261
7 Díez-Martin D.
Kotecha NR.
Ley SV.
Mantegani S.
Menéndez JC.
Organ HM.
White AD.
Banks JB.
Tetrahedron
1992,
48:
7899
8 Behrens CH.
Sharpless KB.
J. Org. Chem.
1985,
50:
5696
9 Ittah Y.
Sasson Y.
Shahak I.
Tsaroom S.
Blum J.
J. Org. Chem.
1978,
43:
4271
10 Åhman J.
Jarevång T.
Somfai P.
J. Org. Chem.
1996,
61:
8148
11 Åhman J.
Somfai P.
Tanner D.
J. Chem. Soc., Chem. Commun.
1994,
2785
12 Åhman J.
Somfai P.
Tetrahedron
1999,
55:
11595
13 Hussenius A.
Somfai P.
Tanner D.
J. Phys. Org. Chem.
1996,
9:
623
14a Olofsson B.
Somfai P.
J. Org. Chem.
2002,
67:
8574
14b Lindström UM.
Somfai P.
Synthesis
1998,
109
15 Burke CP.
Shi Y.
Angew. Chem. Int. Ed.
2006,
45:
4475
16 Barrett AGM.
Seefeld MA.
White AJP.
J. Org. Chem.
1996,
61:
2677
17 Åhman J.
Somfai P.
J. Am. Chem. Soc.
1994,
116:
9781
18 Åhman J.
Somfai P.
Tetrahedron Lett.
1996,
37:
2495
19 Wu Y.-D.
Houk KN.
Marshall JA.
J. Org. Chem.
1990,
55:
1421
20 Somfai P., unpublished results.
21 Ottosson H., Somfai P., unpublished results.
22 Åhman J.
Somfai P.
Tetrahedron Lett.
1995,
36:
303
23 Åhman J.
Somfai P.
Tetrahedron
1995,
51:
9747
24 Daly JW.
Spande TF. In Alkaloids: Chemical and Biological Perspectives
Vol. 5:
Pelletier SW.
Wiley;
New York:
1986.
Chap. 1.
25 Moffett MW.
National Geographic
1995,
187:
98
26 Aronstam RS.
Daly JW.
Spande TF.
Narayanan TK.
Albuquerque EX.
Neurochem. Res.
1986,
11:
1227
27 Anderson JC.
Siddons DC.
Smith SC.
Swarbrick ME.
J. Chem. Soc., Chem. Commun.
1995,
1835
28 Murata Y.
Nakai T.
Chem. Lett.
1990,
2069
29 Kessar SV.
Singh P.
Singh KN.
Kaul VK.
Kumar G.
Tetrahedron Lett.
1995,
36:
8481 . In our hands it has not been possible to repeat the experiments described in this report
30 Coldham I.
Middleton ML.
Taylor PL.
J. Chem. Soc., Perkin Trans. 1
1998,
2817
31a Blid J.
Somfai P.
Tetrahedron Lett.
2003,
44:
3159
31b Blid J.
Brandt P.
Somfai P.
J. Org. Chem.
2004,
69:
3043
32 InCl3 and ZnCl2 gave low yields; other unsuccessful Lewis acids were CuCl, CuCl2 , TiCl4 , Yb(OTf)3 , FeCl3 , ZrCl2 Cp2 , and ScCl3 .
33 Markó IE. In Comprehensive Organic Synthesis
Vol. 3:
Trost BM.
Fleming I.
Pergamon;
Oxford:
1991.
p.913-974
34a Kaiser GV.
Ashbrook CW.
Baldwin JE.
J. Am. Chem. Soc.
1971,
93:
2342
34b Hiroi K.
Nakazawa K.
Chem. Lett.
1980,
1077
34c Clark JS.
Hodgson PB.
Tetrahedron Lett.
1995,
36:
2519
34d Gawley RE.
Zhang Q.
Campagna S.
J. Am. Chem. Soc.
1995,
117:
11817
34e Glaeske KW.
West FG.
Org. Lett.
1999,
1:
31
34f Aggarwal VK.
Fang G.
Charmant JPH.
Meek G.
Org. Lett.
2003,
5:
1757
34g Nakai T.
Tomooka K.
Pure Appl. Chem.
1997,
69:
595
35 Workman JA.
Garrido NP.
Sançon J.
Roberts E.
Wessel HP.
Sweeney JB.
J. Am. Chem. Soc.
2005,
127:
1066
36 Fujimoto K.
Matsuhashi C.
Nakai T.
Heterocycles
1996,
42:
423
37a Cagle PC.
Arif AM.
Gladysz JA.
J. Am. Chem. Soc.
1994,
116:
3655
37b Meyer O.
Cagle PC.
Weickhardt K.
Vichard D.
Gladysz JA.
Pure Appl. Chem.
1996,
68:
79
38 Corey EJ.
Imwinkelried R.
Pikul S.
Xiang YB.
J. Am. Chem. Soc.
1989,
111:
5493
39 Blid J.
Panknin O.
Somfai P.
J. Am. Chem. Soc.
2005,
127:
9352
40 PhMe: 70% yield, er ≥ 98.5:1.5; Et2 O: 27% yield,
41 Blid J.
Panknin O.
Tuzina P.
Somfai P.
J. Org. Chem.
2007,
72:
1294
